CN105601560A - Weak light frequency upconversion triplet state sensitizer and use of sensitizer - Google Patents
Weak light frequency upconversion triplet state sensitizer and use of sensitizer Download PDFInfo
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- CN105601560A CN105601560A CN201511014575.XA CN201511014575A CN105601560A CN 105601560 A CN105601560 A CN 105601560A CN 201511014575 A CN201511014575 A CN 201511014575A CN 105601560 A CN105601560 A CN 105601560A
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- 125000000962 organic group Chemical group 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 230000008859 change Effects 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 18
- 238000001514 detection method Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 230000004044 response Effects 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 3
- 150000003624 transition metals Chemical group 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical group [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052707 ruthenium Chemical group 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 16
- 230000008878 coupling Effects 0.000 abstract description 14
- 238000010168 coupling process Methods 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 6
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical group [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 abstract 1
- 239000007787 solid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004020 luminiscence type Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000005281 excited state Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001748 luminescence spectrum Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical class CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940098773 bovine serum albumin Drugs 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/55—Acids; Esters
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
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Abstract
The invention discloses a weak light frequency upconversion triplet state sensitizer and use of the sensitizer. The molecular structural formula of the sensitizer contains a centre metal element M and an organic group R, wherein the centre metal element M is a transition metal element; the organic group R is carboxyl, amidogen or hydroxyl. The sensitizer disclosed by the invention has a biological coupling group, and can coupling react with biomolecules, so that the sensitizer can be used in the field of detecting biomolecules by weak light frequency upconversion; the organic group can react with polymers so as to connect the sensitizer and the polymers, therefore the invention also discloses application of the weak light frequency upconversion triplet state sensitizer in preparing polymer-based solid weak light upconversion materials.
Description
Technical field
The invention belongs to nonlinear optical material field, be specifically related to the Triplet Sensitizers of a class with coupling group,Can further expand the application of switch technology in low light level frequency by this coupling group.
Background technology
It is a Multiple-quantum process that triplet state-triplet state is buried in oblivion upper conversion (TTA-UC), conventionally need to be by sensitizer and luminousAgent mixes formation triplet state and buries in oblivion upper conversion bicomponent system, based on Triplet Sensitizers and triplet state luminous agent moleculeInterphase interaction produces, and is that low-yield (wavelength is a long) light is converted to the process of high-energy (wavelength is short) light. Its processExactly: i) first sensitizer absorbs after a photon arrives excitation state and arrive its triplet state by intersystem crossing (ISC); Ii) bySensitizer is to triplet state-Triplet energy transfer (TTT) occurs between luminous agent; Iii) two occur in triplet state luminous agentTriplet state-triplet state is buried in oblivion (TTA) and is launched up-conversion fluorescence. The upper transfer process of whole TTA is exactly: sensitizer photon is at baseWhen state, absorb energy, be excited and come single line excitation state, it arrives Triplet Excited State by intersystem crossing, again by three linesTai – Triplet energy transfer, energy is now passed to acceptor (luminous agent) photon, and (sensitizer photon needs and luminous agentCollision transferring energy), make it arrive Triplet Excited State, when in the time that the luminous agent photon of Triplet Excited State reaches finite concentration,Two luminous agent photons in Triplet Excited State are buried in oblivion (collision mutually) by triplet state-triplet state, on certain probability,To produce a luminous agent photon in single line excitation state, another gets back to ground state, now sending out in singlet excitedPhoto etching photo emissions goes out fluorescence and gets back to ground state.
The upper conversion of T-T annihilation (TTA) have required exciting light energy low (peak power for < 0.1W ×cm-2Light intensity can excite), the advantage such as high, the extinction ability of upper conversion quantum efficiency is strong, excitation-emission wavelength is adjustable, at photoelectricityThe field such as device and light reaction has important potential using value, has been subject in recent years extensive concern. Conversion body on TTAIn system, because first the upper transfer process of TTA needs Triplet Sensitizers to absorb external incident light, then by complicatedOptical physics chemical process, (energy is lower than incident light, wavelength generation anti-Stokes position to realize the fluorescent emission of accepting agent moleculeMove phenomenon). Therefore the photophysical property of Triplet Sensitizers is most important for the performance of the upper converting system of whole TTA.
On existing TTA, in converting system, it is chemically inert mostly sensitizer is, do not have further reaction active sitePoint, this has limited the further expansion application of the upper switch technology of TTA greatly. The present invention is intended to for changing and carry in TTA low light level frequencyThere is the Triplet Sensitizers of coupling group for a class.
Summary of the invention
The object of the invention is to bury in oblivion (TTA) upper converting system for triplet state-triplet state provides a class to have coupling groupSensitizer molecule, by coupling reaction, sensitizer can be connected with the realization such as biomolecule, polymeric material, thereby is TTAUpper switch technology provides potential application.
To achieve the above object of the invention, the technical solution used in the present invention is: in a kind of low light level frequency, change triplet state quickAgent, its molecular structural formula contains central metal element M and organic group R; Described central metal element M is transition metal unitElement; Described organic group R is carboxyl, amino or hydroxyl.
In technique scheme, the molecular structural formula of changing Triplet Sensitizers in described low light level frequency is:
Or
In formula, X^Y bidentate ligand, X ˊ ^Y ˊ bidentate ligand are independently selected from C^N bidentate ligand, N^N bidentate ligand or C^C bidentatePart; A is halogen. Organic group R is positioned on bidentate ligand; Halogen A can be chlorine; M is iridium or ruthenium.
In technique scheme, described X^Y bidentate ligand, X ˊ ^Y ˊ bidentate ligand are independently selected from following chemical structural formulaIn one:
。
In preferred technical scheme, the molecular structural formula of changing Triplet Sensitizers in described low light level frequency is following structureThe one of formula:
。
The invention also discloses converting system in a kind of two component low light level frequency, comprise in above-mentioned low light level frequency and change three linesState sensitizer, luminous agent; The mol ratio of described sensitizer and luminous agent is 1: 20～1000. The present invention is also a little less than disclosed pair of componentIn light frequency, changing triplet state system medium used can be organic solvent, ionic liquid, microemulsion etc.; Wherein organic solventCan be toluene, DMF (DMF), chloroform, oxolane (THF), dimethyl sulfoxide (DMSO) (DMSO) etc.
In preferred technical scheme, the molecular structural formula of luminous agent of the present invention is following a kind of:
. In luminous agent structural formula, substituent R1Can be hydrogen orPhenyl.
Sensitizer disclosed by the invention has biological coupling group, can with biomolecule generation coupling reaction, thereby canTo be applied to the detection field of conversion to biomolecule in low light level frequency; Therefore the invention also discloses in above-mentioned low light level frequency and turnChange the application of Triplet Sensitizers in detection of biological molecule.
Sensitizer disclosed by the invention with organic group can with polymer reaction, thereby connect sensitizer and polymerizationThing, therefore the invention also discloses and in above-mentioned low light level frequency, changes Triplet Sensitizers and turn preparing on the solid-state low light level of PolymersApplication in conversion materials.
The invention also discloses the preparation method who changes Triplet Sensitizers in above-mentioned low light level frequency, by the halogen of metal MCompound adds thermal response with the ligand compound that contains organic group R; Then purified separation can obtain in low light level frequencyConversion Triplet Sensitizers.
Such as the halide of the metal M taking chemical formula as MA reacts with the X^Y bidentate ligand with R group; Then with X ˊ ^Y ˊ bidentate ligand adds thermal response, obtains changing Triplet Sensitizers, structure in corresponding low light level frequency finally by crossing purifies and separatesFormula is as follows:
。
The halide of the metal M taking chemical formula as MA with add thermal response with the X^Y bidentate ligand of R group, then pass throughPurifies and separates obtains changing Triplet Sensitizers in corresponding low light level frequency, and structural formula is as follows:
。
Because technique scheme is used, the present invention compared with prior art has following advantages:
The present invention disclose first a kind of with can with the sensitizer molecule of the organic group of biomolecule coupling, its also haveCentral transition metal atom; Can form in two component low light level frequencies and change triplet state system with luminous agent, have excellent a little less thanConversion efficiency on light.
2. in the low light level frequency of sensitizer composition disclosed by the invention, changing compound system can be by sensitizer moleculeCoupling group be connected with biomolecule, in the low light level frequency conversion during the detection of biomolecule is analyzed, have potential shouldWith; Also can realize and being connected with polymer by the coupling group on sensitizer molecule, at the solid-state low light level with polymer substrateUpper conversion field has the value of potential application.
Brief description of the drawings
Fig. 1 is converting system up-conversion luminescence photo figure in two component low light level frequencies of embodiment tetra-;
Fig. 2 is converting system up-conversion luminescence spectrogram in two component low light level frequencies of embodiment tetra-;
Fig. 3 is converting system up-conversion luminescence spectrogram in two component low light level frequencies of embodiment five;
Fig. 4 is converting system up-conversion luminescence spectrogram in two component low light level frequencies of embodiment six;
Fig. 5 is converting system up-conversion luminescence spectrogram in two component low light level frequencies of embodiment six;
Fig. 6 is converting system up-conversion luminescence spectrogram in two component low light level frequencies of embodiment seven.
Detailed description of the invention
Below in conjunction with embodiment, accompanying drawing, the invention will be further described:
In embodiment mono-low light level frequency, change the synthetic of Triplet Sensitizers
By ˊ-butyric acid-2,4-methyl-4,2 ˊ-bipyridyl and ruthenium trichloride join in ethylene glycol ethyl ethers ether solvents, heating reflux reactionAfter 12 hours, solvent is removed, conventional recrystallization has obtained three (ˊ-butyric acid-2,4-methyl-4,2 ˊ-bipyridyls) and has closed ruthenium complex.
。
In embodiment bis-low light level frequencies, change the synthetic of Triplet Sensitizers
C^N part is first prepared to corresponding chlorine bridge complex by reacting with iridous chloride, then further with 4-methyl-4 ˊ-butyric acid-2, the reaction of 2 ˊ-bipyridyl, after 24 hours, obtains following Triplet Sensitizers by purifying.
。
In embodiment tri-low light level frequencies, change the synthetic of Triplet Sensitizers
C^N part is first prepared to corresponding chlorine bridge complex by reacting with iridous chloride, then further with 4-methyl-4 ˊ-butyric acid-2, the reaction of 2 ˊ-bipyridyl, after 24 hours, obtains following Triplet Sensitizers by purifying.
。
Embodiment tetra-
The molecular structural formula of sensitizer is:
The molecular structural formula of luminous agent is:
Sensitizer and luminous agent are dispersed in toluene, are mixed with two component low light levels of different sensitizers and luminous agent mol ratio frequentlyIn rate, change triplet state system. At the low light level, (wavelength is 532nm, and exciting light energy density is after the matchCanObtain blue up-conversion fluorescence, see accompanying drawing 1; Accompanying drawing 2 is for changing the upper conversion of triplet state system in above-mentioned pair of component low light level frequencyLuminescent spectrum, sensitizer and luminous agent mol ratio are the upper conversion efficiency under 1:20,1:200,1:350,1:500,1:600 conditionBe followed successively by 6%, 18%, 22%, 24%, 27%.
Embodiment five
The molecular structural formula of sensitizer is:
The molecular structural formula of luminous agent is:
Sensitizer and luminous agent are dispersed in DMF, are mixed with two component low light levels of different sensitizers and luminous agent mol ratio frequentlyIn rate, change triplet state system. At the low light level, (wavelength is 532nm, and exciting light energy density is after the matchCanObtain blue up-conversion fluorescence; Accompanying drawing 3 is the up-conversion luminescence spectrum of changing triplet state system in above-mentioned pair of component low light level frequency,Along with the increase gradually of luminous agent concentration, upper conversion efficiency can reach 19%.
Embodiment six
The molecular structural formula of sensitizer is:
The molecular structural formula of luminous agent is:
Sensitizer and luminous agent are dispersed in ionic liquid, a little less than being mixed with two components of different sensitizers and luminous agent mol ratioIn light frequency, change triplet state system. At the low light level, (wavelength is 532nm, and exciting light energy density is after the matchCan obtain blue up-conversion fluorescence; Accompanying drawing 4 is changed triplet state system in above-mentioned pair of component low light level frequencyUp-conversion luminescence spectrum, its efficiency can reach 32%.
Get in two component low light level frequencies that sensitizer and luminous agent mol ratio are (1:350) and change triplet state system. Accompanying drawing 5For changing the Up-conversion Intensity of triplet state system and the graph of a relation of laser power in above-mentioned pair of component low light level frequency, at wavelengthFor 532nm, under different laser powers, can obtain blue up-conversion fluorescence.
Embodiment seven
The molecular structural formula of sensitizer is:
The molecular structural formula of luminous agent is:
Carboxyl and bovine serum albumin(BSA) (BSA) molecule by sensitizer carry out coupling, by quick the triplet state with protein molecularAgent is combined with luminous agent and is formed upper converting system, and accompanying drawing 6 is the up-conversion luminescence spectrum of converting system on this, conversion effect on itRate can reach 27.2%. This presentation of results, by the effect of coupling group, can detect upper switch technology and bioanalysis in conjunction with risingCome, sensitizer of the present invention is with a wide range of applications aspect biological detection.
Embodiment eight
By the effect of coupling group, be connected to polymeric material top using Triplet Sensitizers as side chain, further with send outPhoto etching fully mixes, and the composite obtaining also has upper transition effects after testing. Be specially polyvinyl alcohol and enforcementThe sensitizer reaction of example one obtains the polymer of side chain with sensitizer; So by the luminous agent of this polymer and embodiment five according toMol ratio is mixed with converting system at 1: 300, obtains converting system on the solid-state low light level of Polymers, have nearly 25% on turnChange efficiency, higher than 21% upper conversion efficiency of converting system on the solid-state low light level of Polymers of coupling sensitizer not. This result is saidBright by the effect of coupling group, sensitizer can be connected with polymeric material with the form of covalent bond equally, can strengthenInner energy transfer efficiency, the light intensity of conversion in lifting.
Claims (10)
1. in low light level frequency, change a Triplet Sensitizers, it is characterized in that: in described low light level frequency, change triplet state sensitizationThe molecular structural formula of agent contains central metal element M and organic group R; Described central metal element M is transition metal;Described organic group R is carboxyl, amino or hydroxyl.
2. in low light level frequency, change Triplet Sensitizers according to claim 1, it is characterized in that, in described low light level frequencyThe molecular structural formula of conversion Triplet Sensitizers is:
Or
In formula, X^Y bidentate ligand, X ˊ ^Y ˊ bidentate ligand are independently selected from C^N bidentate ligand, N^N bidentate ligand or C^C bidentatePart; A is halogen.
3. in low light level frequency, change Triplet Sensitizers according to claim 1, it is characterized in that: described M is iridium or ruthenium.
4. in low light level frequency, change Triplet Sensitizers according to claim 1, it is characterized in that: described X^Y bidentate ligand,X ˊ ^Y ˊ bidentate ligand is independently selected from the one in following chemical structural formula:
。
5. in low light level frequency, change Triplet Sensitizers according to claim 4, it is characterized in that, in described low light level frequency, turnThe one that the molecular structural formula that changes Triplet Sensitizers is following structural formula:
。
6. a converting system in two component low light level frequencies, comprises described in claim 1～5 and changing in any one low light level frequencyTriplet Sensitizers, luminous agent; The mol ratio of described sensitizer and luminous agent is 1: 20～1000.
7. converting system in two component low light level frequencies according to claim 6, is characterized in that the molecule knot of described luminous agentStructure formula is following a kind of:
。
8. described in claim 1～5, in any one low light level frequency, change Triplet Sensitizers answering in detection of biological moleculeWith.
9. described in claim 1～5, in any one low light level frequency, change Triplet Sensitizers prepare Polymers solid-state a little less thanApplication in light up-conversion.
10. described in claim 1, in low light level frequency, change the preparation method of Triplet Sensitizers: the halide by metal M withThe ligand compound that contains organic group R adds thermal response; Then purified separation can obtain changing three in low light level frequencyLine state sensitizer.
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| CN110724167B (en) * | 2018-09-05 | 2022-09-23 | 苏州科技大学 | Triplet-triplet annihilation up-conversion photosensitizer and application thereof |
| CN116254109A (en) * | 2021-12-09 | 2023-06-13 | 中国科学院大连化学物理研究所 | Triplet state-triplet state annihilation up-conversion method for visible light to ultraviolet light |
| CN116254109B (en) * | 2021-12-09 | 2024-02-23 | 中国科学院大连化学物理研究所 | Triplet state-triplet state annihilation up-conversion method for visible light to ultraviolet light |
| WO2023184998A1 (en) * | 2022-03-31 | 2023-10-05 | 苏州科技大学 | Method for determining fitted ternary phase diagram of microemulsion by means of fluorescence method |
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